A method for directly converting fructose into hexanedione compounds

Abstract

The present invention belongs to the field of heterogeneous catalytic reaction processes, and in particular relates to a method for directly converting fructose into hexanedione compounds using a bifunctional heterogeneous catalyst. The method comprises subjecting fructose and H2 to the direct conversion in a reactor in the presence of the bifunctional heterogeneous catalyst to the direct conversion into hexanedione compounds, thereby avoiding the purification and separation process of 5-hydroxymethylfurfural in the traditional route. The method uses a bifunctional heterogeneous catalyst, and the reaction process and apparatus are simple. The catalyst has excellent reactivity and stability, reduces the separation cost of the catalyst from reactants and products, and effectively improves the economic benefits of the direct conversion of fructose into hexanedione compounds. The reaction product hexanedione compounds include 2,5-hexanedione and 1-hydroxy-2,5-hexanedione, which are new platform compounds widely used in the fields of medicine, fragrances, aviation fuel, and synthetic chemistry.

Description

Technical Field

[0001] The invention belongs to the field of heterogeneous catalytic reaction technology, and particularly relates to a method for directly converting sugars into hexanedione compounds by using a bifunctional heterogeneous catalyst. Background Art

[0002] Biomass energy is the only renewable carbon resource that can replace fossil energy by converting it into liquid and gaseous fuels, as well as other chemical raw materials or products. Biomass energy, which is solar energy stored in biomass as chemical energy, has long been a vital energy source for human survival, ranking fourth after coal, oil, and natural gas, and occupying a crucial position in the overall energy system. With the depletion of fossil energy and humanity's growing concern about global environmental issues, the research and development of biomass energy as an alternative to fossil energy has become a hot topic of research and attention for many scholars both domestically and internationally.

[0003] The derivatization of carbohydrates is a crucial component of biomass energy utilization. Typically, carbohydrate compounds are first dehydrated over an acidic catalyst to produce 5-hydroxymethylfurfural (5-HMF). As a platform compound, 5-HMF can be further synthesized through hydrogenation, oxidation, and condensation reactions to yield a variety of valuable derivatives, including 2,5-dimethyltetrahydrofuran (2,5-DMTHF), 2,5-dimethylfuran (2,5-DMF), 5-methylfurfural (5-MF), 2,5-furan dimethanol (BHMF), 2,5-furandicarboxylic acid (2,5-FDCA), 2,5-hexanedione, and 1-hydroxyhexane-2,5-dione (HHD). These derivatives are widely used in pharmaceuticals, fragrances, aviation fuels, and synthetic chemistry. Among these, hexanedione compounds, including 2,5-hexanedione and 1-hydroxy-2,5-hexanedione, are attracting increasing attention from researchers due to their potential as novel platform compounds. However, the primary production pathway for hexanediones currently involves dehydrating sugars to produce 5-HMF. After separation and purification, 5-HMF is then derivatized to hexanediones in the presence of a catalyst. Currently, there is limited research on the direct conversion of sugars to hexanediones. Furthermore, direct conversion of sugars to hexanediones primarily occurs in homogeneous reactions. To achieve this, a catalyst with both acidic and metal active sites is required.

[0004] In summary, the plan is to leverage the ease of modification of porous organic polymers to prepare multifunctional solid heterogeneous catalysts through post-modification. This simplifies the reaction process, avoids the separation and purification of platform compounds, and directly converts sugars to hexanedione compounds as the final product. The development of efficient, recyclable, green, and clean catalysts is a major research direction in this field. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide a process for directly preparing hexanedione compounds by heterogeneous catalytic conversion of sugars with excellent reactivity and stability that can be easily implemented industrially.

[0006] To this end, the present invention provides a method for directly converting fructose to produce hexanedione compounds, characterized in that the method uses a solid heterogeneous catalyst, which is composed of a metal component and an acidic P-containing organic ligand polymer, wherein the metal component is one or more of metals Pd and Pt, and the acidic P-containing organic ligand polymer is a porous polymer with a large specific surface area generated by solvent thermal polymerization of a vinyl-functionalized phosphine ligand monomer, which is then modified by reaction with 1,3-propane sultone and then loaded with acid to obtain the polymer. The metal component forms a coordination bond with the P atoms in the organic ligand polymer skeleton and is highly dispersed and stably present on the organic ligand polymer carrier. The method comprises reacting fructose and hydrogen in a reactor in the presence of the solid heterogeneous catalyst to directly convert the fructose to produce hexanedione compounds.

[0007] In a preferred embodiment, the vinyl functionalized phosphine ligand monomer is selected from one or more of the following:

[0008]

[0009] In a preferred embodiment, the fructose is selected from one or two of the following:

[0010]

[0011] In a preferred embodiment, the reactor is a tank reactor, a fixed bed reactor, a trickle bed reactor or a fluidized bed reactor; when the reactor is a tank reactor, the molar ratio of the fructose raw material to the H2 raw material is 1:1-1:200; when the reactor is a fixed bed reactor, a trickle bed reactor or a fluidized bed reactor, fructose is transported into the reactor in the form of an aqueous solution using a high-pressure pump, the concentration of the fructose aqueous solution is 0.1-100 g / L, and the liquid hourly space velocity is 0.01-5h -1 , H2 is fed directly in gas form, with a gas space velocity of 500-10000h -1 .

[0012] In a preferred embodiment, the direct conversion of fructose to produce hexanedione compounds is carried out in an intermittent or continuous manner. When the reactor is a tank reactor, the direct conversion of fructose to produce hexanedione compounds is carried out intermittently, and the liquid product generated in the tank reactor is filtered, separated from the solid heterogeneous catalyst, and then further processed by distillation or flash evaporation to obtain high-purity hexanedione compounds. When the reactor is a fixed-bed reactor, a trickle-bed reactor, or a fluidized-bed reactor, the direct conversion of fructose to produce hexanedione compounds is carried out continuously, and the resulting liquid product is directly processed by distillation or flash evaporation to obtain high-purity hexanedione compounds.

[0013] In a preferred embodiment, the reaction temperature of the direct conversion of fructose to produce hexanedione compounds is 333-523K, and the reaction pressure is 0.1-15MPa.

[0014] In a preferred embodiment, the metal component accounts for 0.01-8.0% of the total weight of the solid heterogeneous catalyst, and the molar ratio of fructose to the metal active component is 100:1-2000:1.

[0015] In a preferred embodiment, the specific surface area of the acidic P-containing organic ligand polymer is 500-2200 m 2 / g, pore volume of 0.1-4.0cm 3 / g, and the pore size distribution is 0.1-200.0nm.

[0016] Inert gas atmosphere: one or more of argon, helium, nitrogen, and neon.

[0017] In a preferred embodiment, the direct conversion of fructose to produce hexanedione compounds is carried out intermittently, the generated liquid product is separated from the solid heterogeneous catalyst by filtration, and the obtained liquid product is further treated by distillation or flash evaporation to obtain a high-purity difunctionalized aldehyde product.

[0018] The beneficial effects of the present invention include but are not limited to the following aspects: Compared with the existing technology, the reaction technology of directly converting fructose to produce hexanedione compounds of the present invention uses a new solid multiphase catalyst, has a simple reaction process and equipment, and the catalyst has excellent reaction activity and stability, which reduces the cost of separating the catalyst from the reactants and products, effectively improves the economic benefits of the reaction process of directly converting fructose to produce hexanedione compounds, and has broad industrial application prospects. DETAILED DESCRIPTION

[0019] To better illustrate the catalyst preparation method and its application in the direct conversion of fructose to hexanedione compounds, the following examples illustrate the preparation of several catalyst samples and their application in the reaction process. However, the present invention is not limited to these examples. Unless otherwise specified, all contents and percentages in this application are calculated by mass.

[0020] Example 1

[0021] The solvent reservoir was evacuated using a vacuum pump and then filled with argon, repeating this process three times. Then, at 298K, 10.0g of tri(4-vinylphenyl)phosphine ligand, 0.25g of azobisisobutyronitrile (a free radical initiator), and 100ml of tetrahydrofuran were added to the solvent reservoir. After sealing, the mixture was stirred for 0.5 hours. The solvent reservoir was transferred to a 373K oil bath and allowed to stand for 24 hours for polymerization. After cooling to room temperature, the solvent was removed under vacuum at 333K to obtain a porous organic polymer containing phosphine.

[0022] Under an argon atmosphere, 1.0 g of the phosphine-containing porous organic polymer prepared above was dispersed in a round-bottom flask containing 30 ml of toluene solvent. A 10 ml toluene solution containing 0.17 g of 1,3-propane sultone was then added to the flask and stirred at 373 K for 24 hours. After cooling to 273 K, 10 ml of a toluene solution containing 0.21 g of trifluoromethanesulfonic acid was added dropwise, and the mixture was stirred for 24 hours. The solvent was removed under vacuum at 333 K to obtain the acidic organic ligand polymer. At 298 K under an argon atmosphere, 0.0105 g of palladium acetate was dissolved in 40 ml of tetrahydrofuran solvent, and 1.0 g of the acidic porous organic ligand polymer prepared above was added. The mixture was stirred for 24 hours, and the solvent was removed under vacuum at 333 K to obtain a multifunctional solid heterogeneous catalyst loaded with 0.5 wt% metal components and 1.6 mmol / g of acid.

[0023] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor. 0.10 g of Si and 15 ml of tetrahydrofuran were added sequentially. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to raise the autoclave system pressure to 2 MPa. The temperature was then slowly raised to 140°C using a temperature controller and allowed to react for 2 h. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, adding dodecane as an internal standard. The reaction evaluation results are shown in Table 1.

[0024] Example 2

[0025] The catalyst preparation process is the same as that in Example 1, except that 0.0087 g of platinum chloride is used instead of 0.0105 g of palladium acetate in the catalyst preparation. The metal loading is 0.5 wt %.

[0026] Catalyst Evaluation The reaction process was the same as in Example 1. The reaction evaluation results are shown in Table 1.

[0027] Example 3

[0028] The preparation process of the catalyst is the same as that in Example 1.

[0029] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor. 0.15 g of S2 and 15 ml of tetrahydrofuran were added sequentially. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H2. H2 was then introduced to raise the autoclave system pressure to 2 MPa. The temperature was then slowly raised to 140°C using a temperature controller and allowed to react for 2 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, adding dodecane as an internal standard. The reaction evaluation results are shown in Table 1.

[0030] Example 4

[0031] The preparation process of the catalyst is the same as that of Example 1.

[0032] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor. 0.10 g of Si and 15 ml of toluene solvent were added sequentially. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced, and the autoclave system pressure was raised to 1 MPa. The temperature was slowly raised to 140°C using a temperature controller and the reaction was continued for 2 h. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, adding dodecane as an internal standard. The reaction evaluation results are shown in Table 1.

[0033] Example 5

[0034] The preparation process of the catalyst is the same as that of Example 1.

[0035] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor. 0.10 g of Si and 15 ml of toluene solvent were added sequentially. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to raise the autoclave system pressure to 4 MPa. The temperature was then slowly raised to 140°C using a temperature controller and allowed to react for 2 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, adding dodecane as an internal standard. The reaction evaluation results are shown in Table 1.

[0036] Example 6

[0037] The preparation process of the catalyst is the same as that of Example 1.

[0038] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor. 0.10 g of S1 and 15 ml of tetrahydrofuran were added sequentially. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to raise the autoclave system pressure to 2 MPa. The temperature was then slowly raised to 140°C using a temperature controller and allowed to react for 4 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, adding dodecane as an internal standard. The reaction evaluation results are shown in Table 1.

[0039] Example 7

[0040] The preparation process of the catalyst is the same as that of Example 1.

[0041] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor. 0.10 g of Si and 15 ml of tetrahydrofuran were added sequentially. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to raise the autoclave system pressure to 2 MPa. The temperature was then slowly raised to 140°C using a temperature controller and the reaction was continued for 6 h. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, with dodecane added as an internal standard. The reaction evaluation results are shown in Table 1.

[0042] Example 8

[0043] The preparation process of the catalyst is the same as that of Example 1.

[0044] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor. 0.10 g of S1 and 15 ml of tetrahydrofuran were added sequentially. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to raise the autoclave system pressure to 2 MPa. The temperature was then slowly raised to 100°C using a temperature controller and allowed to react for 4 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, adding dodecane as an internal standard. The reaction evaluation results are shown in Table 1.

[0045] Example 9

[0046] The preparation process of the catalyst is the same as that of Example 1.

[0047] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor. 0.10 g of Si and 15 ml of tetrahydrofuran were added sequentially. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to raise the autoclave system pressure to 2 MPa. The temperature was then slowly raised to 120°C using a temperature controller and allowed to react for 4 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, adding dodecane as an internal standard. The reaction evaluation results are shown in Table 1.

[0048] Example 10

[0049] The preparation process of the catalyst is the same as that of Example 1.

[0050] 0.030 g of the solid heterogeneous catalyst prepared in Example 1 was charged into an autoclave reactor, followed by 0.10 g of Si and 15 ml of tetrahydrofuran. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to the autoclave system, maintaining a pressure of 2 MPa. The temperature was slowly raised to 160°C using a temperature controller and the reaction was continued for 4 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, with dodecane added as an internal standard. The reaction evaluation results are shown in Table 1.

[0051] Comparative Example 1

[0052] The catalyst preparation process is the same as that in Example 1, except that 0.0130 g of ruthenium chloride is used instead of 0.0105 g of palladium acetate in the catalyst preparation. The metal loading is 0.5 wt %.

[0053] 0.030 g of the solid heterogeneous catalyst prepared above was charged into an autoclave reactor, followed by 0.10 g of S1 and 15 ml of tetrahydrofuran. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to the autoclave system, maintaining a pressure of 2 MPa. The temperature was slowly raised to 120°C using a temperature controller and the reaction was continued for 4 h. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, with dodecane added as an internal standard. The reaction evaluation results are shown in Table 1.

[0054] Comparative Example 2

[0055] The catalyst preparation process is the same as that in Example 1, except that 0.0083 g of iridium chloride is used instead of 0.0105 g of palladium acetate in the catalyst preparation. The metal loading is 0.5 wt %.

[0056] 0.030 g of the solid heterogeneous catalyst prepared above was charged into an autoclave reactor, followed by 0.10 g of S1 and 15 ml of tetrahydrofuran. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to the autoclave system, maintaining a pressure of 2 MPa. The temperature was slowly raised to 120°C using a temperature controller and the reaction was continued for 4 h. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, with dodecane added as an internal standard. The reaction evaluation results are shown in Table 1.

[0057] Comparative Example 3

[0058] The catalyst preparation process is the same as that in Example 1, except that the P-containing organic ligand polymer is not modified and not loaded with acid during the catalyst preparation process. The metal loading is 0.5 wt%.

[0059] 0.030 g of the solid heterogeneous catalyst prepared above was charged into an autoclave reactor, followed by 0.10 g of S1 and 15 ml of tetrahydrofuran. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to the autoclave system, maintaining a pressure of 2 MPa. The temperature was slowly raised to 120°C using a temperature controller and the reaction was continued for 4 h. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, with dodecane added as an internal standard. The reaction evaluation results are shown in Table 1.

[0060] Table 1 Evaluation results of the reaction of direct conversion of sugars to prepare hexanedione compounds

[0061]

[0062]

[0063] Comparative Examples 1, 2, and 3 provide reaction data for the direct conversion of fructose to hexanedione compounds catalyzed by catalysts with metal components of Ru, Ir, and P-containing organic ligand polymers without acid loading. The catalyst preparation processes for Comparative Examples 1, 2, and 3 are different from those in Example 1, but the other conditions are the same. When the metal component is Ru (Comparative Example 1), the yield of 2,5-hexanedione is 1% and the yield of 1-hydroxy-2,5-hexanedione is 2%. When the metal component is Ir (Comparative Example 2), the yield of 2,5-hexanedione is 2% and the yield of 1-hydroxy-2,5-hexanedione is 2%. When the catalyst is not loaded with acid (Comparative Example 3), no 2,5-hexanedione and 1-hydroxy-2,5-hexanedione production is detected. When the catalyst metal component is Pd and loaded with acid (Example 9), the yield of 2,5-hexanedione is 21% and the yield of 1-hydroxy-2,5-hexanedione is 29%. In summary, the present method, using a multifunctional solid heterogeneous catalyst, can directly convert sugars to produce high-yield hexanedione compounds, simplifying the reaction process and avoiding the need for isolation and purification of platform compounds. This method can shorten the fructose conversion reaction process, effectively simplifying the reaction steps and industrial reaction energy consumption, and has significant economic benefits and practical application value.

[0064] While the present invention has been described in detail above, the present invention is not limited to the specific embodiments described herein. Those skilled in the art will appreciate that other modifications and variations may be made without departing from the scope of the present invention. The scope of the present invention is defined by the appended claims.

Claims

1. A method for directly converting fructose into hexanedione compounds, characterized in that: fructose and H2 are reacted in a reactor in the presence of a catalyst to produce hexanedione compounds, wherein the hexanedione compounds include 2,5-hexanedione and / or 1-hydroxy-2,5-hexanedione; The catalyst is composed of a metal active component and an acidic P-containing organic ligand polymer, wherein the metal active component is selected from one or both of Pd and Pt, and the metal active component forms a coordination bond with the P atoms on the surface of the acidic P-containing organic ligand polymer, thereby being dispersed on the polymer surface; The fructose is selected from one or two of the following: ， The acidic P-containing organic ligand polymer is an organic ligand polymer obtained by solvent thermal polymerization of a vinyl-functionalized phosphine ligand monomer to generate a porous polymer, which is then modified and loaded with an acid. The vinyl-functionalized phosphine ligand monomer is selected from one or more of the following: 。 2. The method according to claim 1, characterized in that The fructose direct conversion reaction temperature is 333-523 K, and the H2 reaction pressure is 0.1-15.0 MPa.

3. The method according to claim 2, characterized in that The fructose direct conversion reaction temperature is 353-473 K, and the H2 reaction pressure is 1-5.0 MPa.

4. The method according to claim 1, wherein When the reactor is a tank reactor, the fructose raw material is directly fed into the reactor, and the molar ratio of the fructose raw material to the H2 raw material is 1:1-1:200; the molar ratio of the fructose raw material to the metal active component is 100:1-2000:

1.

5. The method according to claim 4, characterized in that When the reactor is a tank reactor, the fructose raw material is directly fed into the reactor, and the molar ratio of the fructose raw material to the H2 raw material is 1:10-1:50; the molar ratio of the fructose raw material to the metal active component is 300:1-800:

1.

6. The method according to claim 1, characterized in that When the reactor is a fixed bed reactor, a trickle bed reactor or a fluidized bed reactor, fructose is transported into the reactor in the form of an aqueous solution using a high-pressure pump. The concentration of the fructose aqueous solution is 0.1-100 g / L, and the liquid hourly space velocity is 0.01-5 h -1 ; H2 is fed directly in gas form with a gas space velocity of 500-10000h -1 .

7. The method according to claim 6, characterized in that When the reactor is a fixed bed reactor, a trickle bed reactor or a fluidized bed reactor, fructose is transported into the reactor in the form of an aqueous solution using a high-pressure pump. The concentration of the fructose aqueous solution is 1-10 g / L, and the liquid hourly space velocity is 0.05-1 h -1 ; H2 is fed directly in gas form with a gas space velocity of 1000-5000 h -1 .

8. The method according to claim 4 or 6, characterized in that When the reactor is a tank reactor, the direct conversion of fructose to produce hexanedione compounds is carried out intermittently, and the liquid product generated in the tank reactor is filtered and separated from the catalyst, and then further treated by distillation or flash evaporation to obtain high-purity hexanedione compounds; When the reactor is a fixed bed reactor, a trickle bed reactor or a fluidized bed reactor, the direct conversion of fructose to produce hexanedione compounds is carried out continuously, and the obtained liquid product is directly further treated by distillation or flash evaporation to obtain high-purity hexanedione compounds.

9. The method according to claim 1, characterized in that The metal active component accounts for 0.01-8.0% of the total weight of the catalyst, and the acid loading amount in the catalyst is 0.1-2.0 mmol / g.

10. The method according to claim 9, characterized in that The metal active component accounts for 0.5-4.0% of the total weight of the catalyst, and the acid loading amount in the catalyst is 1.0-1.8 mmol / g.

11. The method according to claim 1, wherein The specific surface area of the acidic P-containing organic ligand polymer is 500-2200m 2 / g, pore volume of 0.1-4.0cm 3 / g, and the pore size distribution is 0.1-200.0 nm.

12. The method according to claim 1, characterized in that Polymerization process of acidic P-containing organic ligand polymer: a) evacuating a solvent storage bottle and then filling it with an inert gas, then adding a phosphine ligand monomer, with or without a crosslinking agent, a free radical initiator, and an organic solvent to the solvent storage bottle at a temperature of 253-323 K, sealing the bottle, and stirring the mixture for 0.1-24 h; The molar ratio of the phosphine ligand monomer to the free radical initiator is 200:1 to 10:1, and the concentration of the phosphine ligand monomer in the organic solvent before polymerization into an organic polymer is in the range of 0.01 to 500 g / L; In the case where a cross-linking agent is added to the phosphine ligand monomer in step a), the molar ratio of the phosphine ligand monomer to the cross-linking agent is 0.01:1 to 10:1; b) placing the solvent storage bottle in step a) at a temperature of 333K-473K for 6-96 hours to carry out a polymerization reaction; cooling to room temperature after the polymerization, and removing the solvent in vacuo at 293-423K to obtain an organic polymer having a hierarchical pore structure and containing exposed P; c) under an inert gas atmosphere, dispersing the organic polymer obtained in step b) in a container containing a solvent, then adding a solution of 1,3-propane sultone to the container, stirring at 273-473 K for 0.5-100 hours, cooling to 223-373 K, then dropwise adding an acid solution, and stirring under an inert gas atmosphere for 0.5-100 hours; then removing the solvent under vacuum at a temperature of 273-473 K to obtain an acidic P-containing organic ligand polymer; Before the 1,3-propane sultone solution is added, the concentration of the organic polymer in the solvent is 1-100 g / L; the concentration of the 1,3-propane sultone solution is 1-50 g / L; the concentration of the acid solution is 1-50 g / L; the molar ratio of the organic polymer to the 1,3-propane sultone is 200:1-1:3; and the molar ratio of the organic polymer to the acid is 200:1-1:

3. The organic solvent in steps a) and c) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform; The free radical initiator in step a) is one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile; The acid used in step c) is one or more of trifluoromethanesulfonic acid, hydrochloric acid, phosphoric acid, phosphotungstic acid, sulfuric acid, silicotungstic acid, trifluoroacetic acid, and p-toluenesulfonic acid; In steps a) and c) the inert gas is one or more of nitrogen, argon, neon and helium.

13. The method according to claim 12, characterized in that Polymerization process of acidic P-containing organic ligand polymer: a) evacuating a solvent storage bottle and then filling it with an inert gas, then adding a phosphine ligand monomer, with or without a crosslinker, a free radical initiator, and an organic solvent to the solvent storage bottle at a temperature of 273-303 K, sealing the bottle, and stirring the mixture for 0.1-3 hours; The molar ratio of the phosphine ligand monomer to the free radical initiator is 50:1-10:1, and the concentration of the phosphine ligand monomer in the organic solvent before polymerization into the organic polymer is in the range of 10-200 g / L; In the case where a cross-linking agent is added to the phosphine ligand monomer in step a), the molar ratio of the phosphine ligand monomer to the cross-linking agent is 1:1-5:1; b) placing the solvent storage bottle in step a) at a temperature of 353-423 K for 8-36 hours to carry out a polymerization reaction; cooling to room temperature after the polymerization, and removing the solvent in vacuo at 323-373 K to obtain an organic polymer having a hierarchical pore structure and containing exposed P; c) under an inert gas atmosphere, dispersing the organic polymer obtained in step b) in a container containing a solvent, then adding a solution of 1,3-propane sultone to the container, stirring at 343-393 K for 18-36 hours, cooling to 253-303 K, then dropwise adding an acid solution, and stirring under an inert gas atmosphere for 18-36 hours; then removing the solvent under vacuum at a temperature of 323-373 K to obtain an acidic P-containing organic ligand polymer; Before the 1,3-propane sultone solution is added, the concentration of the organic polymer in the solvent is 10-50 g / L; the concentration of the 1,3-propane sultone solution is 10-30 g / L; the concentration of the acid solution is 10-30 g / L; the molar ratio of the organic polymer to the 1,3-propane sultone is 10:1-1:2; and the molar ratio of the organic polymer to the acid is 10:1-1:

2.

14. The method according to claim 1, wherein The catalyst preparation process is as follows: placing the acidic P-containing organic ligand polymer in a solvent containing an active metal component, stirring at 273-373K under an inert gas atmosphere for 0.5-72 hours, and then drying at 323-403K to obtain the catalyst; The solvent is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform; The inert gas is one or more of nitrogen, argon, neon and helium.

15. The method according to claim 14, characterized in that The catalyst preparation process is as follows: placing the acidic P-containing organic ligand polymer in a solvent containing an active metal component, stirring at 298K-353K under an inert gas atmosphere for 24-36 hours, and then drying at 333K-373K to obtain the catalyst.

Images